%0 Journal Article
%A Gonzalez-de-Castro, Angela
%A Xiao, Jianliang
%D 2015
%T Green
and Efficient: Iron-Catalyzed Selective Oxidation
of Olefins to Carbonyls with O2
%U https://acs.figshare.com/articles/journal_contribution/Green_and_Efficient_Iron_Catalyzed_Selective_Oxidation_of_Olefins_to_Carbonyls_with_O_sub_2_sub_/2154343
%R 10.1021/jacs.5b03956.s001
%2 https://acs.figshare.com/ndownloader/files/3788194
%K Efficient
%K formation
%K chemoselectivity
%K Olefin
%K species
%K pyridine bisimidazoline ligand
%K olefins
%K Oxidation
%K Catalyzed
%K mechanism
%K Fe
%K iron center
%K 1 atm
%K benzaldehyde
%K carbonyl product
%K oxidation
%K Various observations
%K olefinic substrate
%K carbonyl compounds
%K halo
%K halide migration
%K group tolerance
%K Carbonyl
%K yield
%K ketone
%K acetophenone
%K styrene
%K O 2A
%K dioxetane
%X A mild and operationally simple iron-catalyzed
protocol for the
selective aerobic oxidation of aromatic olefins to carbonyl compounds
is described. Catalyzed by a Fe(III) species bearing a pyridine bisimidazoline
ligand at 1 atm of O2, α- and β-substituted
styrenes were cleaved to afford benzaldehydes and aromatic ketones
generally in high yields with excellent chemoselectivity and very
good functional group tolerance, including those containing radical-sensitive
groups. With α-halo-substituted styrenes, the oxidation took
place with concomitant halide migration to afford α-halo acetophenones.
Various observations have been made, pointing to a mechanism in which
both molecular oxygen and the olefinic substrate coordinate to the
iron center, leading to the formation of a dioxetane intermediate,
which collapses to give the carbonyl product.
%I ACS Publications